Compound from indene and phenols



Patented is, s, 1930 1 UNITED [STATES PATENT? optic];

LEO ROBENTHAL, OF VOHWINKEL, AND WALTER KBOPP, OF ELBERFELD, GERMANY,ASSIGNORS TO I. G. FABIBENIND'USTBIE AKTIENGESELLSGHAIT, OF FRANKFURT-ON-THE-MAIN', GERMANY comounn anon mnnnn am) rnnnons 1T0 Drawing.Application fll'ed J'une 22, 1927, Serial No. 200,761, and in GermanyJune 28, 1926.

The present invention relates to new compounds of the indene series andto a process of pre aring same.

We ave found that new valuable compounds are obtained by causing ahalogen .acid to act upon a mixture ofan indene compound and a phenolcompound. -One may '.us e, for instance, as reaction components indene,such derivativesof indene as are sub-- stituted in a-position or anyother indene derivative and on the other hand henol, .cresol, amino-,nitro-, or chloro-p enols, thymol, naphthols, 'polyvalent phenols suclras pyrocatechin, resorcin and the like It is not necessary to use. thereaction components I in a pure state, but one may use crude substancescontaining either an indene com pound or a phenol compound,respectively. For instance, instead of indene one may use 2o the crudebenzene fraction distilling at a temperature of about 160-190 C. at roomtemperature. The reaction proceeds in the resence of small quantities ofhalogen aci s or metal chlorides, inmost cases also at ordinartemperature and frequently with the evo ution of heat. The halogen acidcan be employed in the gaseous form or in aqueous or alcoholic"solutions and the metal chlorides asanhydrous salts or in the form ofaqueous .30 or alcoholic solutions.- Instead of a halogen acid one mayuse ferric chlorides which act in an equivalent manner. H l The newproductsobtained in accordance with'the present'invention areintended tofind application forgtherapeutical purposes, as disinfectants, as, basesfor the manufacture of lacquers, as intermediate products for themanufacture of dyestuffs and the like.

They are viscous oils which can be distilled in vacuo. They re solublein alcohol, benzene, ethyl acetate, butyl acetate or the like. Theyrepresent mostly a mixture of several compounds. By extracting them withdiwhich correspond probably to the general formula: l

The alkali-insoluble part" represents oondensation products probablycontaining ether-bondages the structure The following examples willillustrate our invention, which is wide limits:-- l

Ewample 1.To a mixture ofi6 parts by weight of indene and 5 parts byweight of phenol, 2 parts by weight of concentrated hydrochloric acidare addedwith stirring. A highly viscous oil separates with stronrevolution of heat, the h drochloric acid an small quantities of uncanged startingv material being removed in the known manner. In order toeffect purification the reaction product can be distilled in vacuo.. Alight g of which, however, is not definitely known.

applicable within very i colored oil, soluble in very many organicsolvents is obtained, distilling at above 180 0. under 9 mm. pressurecInstead of concentrated hydrochloric acid an alcoholic hydm chloric acidsolution can be employed, in which case stirring of the reaction mixtureis not necessary.

Instead of the above mentioned. quantity of indene the correspondingquantity of crude solvent naphtha can be employed, containing the sameamount of indene and from which-bases and phenols have preferably beenremoved.

The oil, which boils above 180 C. and

. luene or other suitable hydroaromatic hydro 5 luted alkali lyesubstances may be obtained Ecarbon, from which solution a substance sooncrystallizes in a pure state possessing a melt-. ing point of 88 C. Fromits chemical behavior and analysis the new product is probably hdrindylphenol (oxyp enylindane) of the fo owing constitut1on:

There remains in the mother liquor a reaction product, insoluble inalkali, which on the elimination of the solvent constitutes a highlyviscous 1i ht colored oil.

disinfecting action hydrindyllphenol iswell suited to application for tEcmrmpk 2.A mixture of 300 parts by weight of crude benzene, boilinbetween 160-190 C. are stirred for several ours with 100-150 parts bweight of crude cresol with the addition 0 20 parts by weight of 20%hydrochloric acid, whereupon the mixture is washed until free from acidand then sub- Leicted to vacuum distillation. A light colored 'ghlyviscous oil, boiling at 180 to 230 C.

erapeutic purunder 9 mm., is obtained together with a small quantity ofa light colored resin, which is completely soluble in alcohol and can beemployed for the manufacture of s iri't lacquers and the like, Theviscous 01]. can be resolved into an alkali soluble and an alkaliinsoluble portion.

Example 8. parts by wei ht of indene are mixed with parts by weig t ofa-naphtholand3to5partsbywe' htofa%% alcoholic h drochloric acid so utionare introduced. en the reaction is com late the unchanged naphthol isremoved wi dilute caustic soda lye. About 110 arts by weight areobtained of an alcohol so uble, alkali msoluble oil, which is highlyviscous at ordinary temperature.

Example 4-600 parts by weight of crude benzene (distillation limits160-185 C.) are mixed with 100 parts by weight ofcrude cresol. Intothe'mixture 40 parts b weight of crystalline ferric chloride or a so utionof 20 parts by weight of anhydrous ferric chloride in 20 parts weight ofalcohol are added and the who e is stirred for several hours. The ferricchloride is removed in known manner and after distillation in vacuo ofthe en .200 grams of'this phenol volatile portion (up to 180 C.), alight col .ored resm is obtained, which melts at about -110 0. and issoluble in warm alcohol. On the addition of small quantities of butylalcohol or oil of turpentine to the alcoholic resin solution noseparation of the resin occurs even at rd'mary temperature.

Ewample .A mixture of 221 parts by weight of alylindene, 108 parts byweight of cresol or p enol and 20 parts by weight of concentratedhydrochloric acid are stirred for several hours. After the working up ofthe reaction product as described in Example 2 a highly viscous oil isobtained, which is insoluble in alkali and boils at 200 to 250 C. under10 mm. pressure.

Example 6'.100 parts by weight of an indene fraction having a content of49% indene are mixed with 46 parts by weight of o-cresol. To thissolution 5 partsby wei ht of concentrated hydrochloric'acid are ad ed.

The temperature thereby rises from 22 to about 40 0. As a result of thisreaction there is produced together with a highlyviscous alkaliinsoluble oil an alkali soluble substance which crystallizes well andphenolic character, which on an ysis a pears to be hydrindyl-o-cresol ofthe probab e formula m. m is This substance is obtained b extracting thereaction liquid advantageo y after dilution with benzene with dilutecaustic soda lye, acidi the alkaline solution, separating the resultingoil and distilling the mixture of unchanged o-cresol andhydrindyl-o-cresol in vacuo. From the fraction which p a over between200-230 C. under 10 mm. th .hydrindyl-o-cresol is obtained by recstallization from cyclohexane in well dev oped c stals of point 63 C.

en the reaction solution extracted with caustic soda lye is inyacuounder 10 mm. pressure, a. highly viscous oil 1 :1 over above 180 0.,which is soluble in alcohol and benzene in all proportions and findsapplication for purposes.

Example 7.A mixture of 250 parts by weight of an indene fraction with acontent of 50% of indene and 130 parts by weight of resorcinol is heatedto 85-40 C. with brisk 10 to 20 parts by weight of alcoholichydrochloric acid solution of 20% HO].

ture is reduced to 7080 C. and then the m whole is diluted with 300 to400 parts by temperature in vacuo, and being generally solu lein organicsolvents.

In testimony whereof we have hereunto set weight of benzene.

This solution is then extracted "with dilute alkali lye. From thealkaline solution a viscous oil is precipitated on acidification whichis purified from small quantities of 'unchanged resorcin by repeatedstirring with Water. The oil, free from resorcin, is thereupon subjectedto vacuum distillation: A viscous oil is thus obtained in very goodyield. It distils at 220260 C. under 2 mm.

I and solidifies on cooling to a lighttransparout mass. This massappears to be a mixture of several substances possessing phenolcharacter and can be employed for the manufacture of lacquers and thelike and other purposes.

The term indenic compound is used in the following claims to denoteindene and its homologues and substitution'products either singly or inadmixture, and the term phenolic compound is used to denote aromaticcompounds containing one or more hydroxyl groups'attached to the organicnucleus, and their homologues and substitution products either singly orin admixture.

1. The process which comprises causing a halogen acid to act upon amixture of an indeniccompound and a phenolic compound. 2. The processwhich comprises causing.

hydrochloric acid to act upon a mixture of our hands.

an indenic compound and a phenolic com- I pound.

3. The process which comprises causing hydrochloric acid to act upon amixture of indene and phenol.

4. As new products the compounds of the general formula:

I I v H fi H 3 E1 wherein R represents an aromatic nucleus substitutedby at least one hydroxyl group.

5; Ass. new product the compound of the general formula: p

melting at 88C. and forming with hexafmethylenetetraminea substancemelting at ,6. As new products, reaction products of phenolic compoundswith indemc compounds whlch are obtainable by causing ahalogen a I acidto .act upon a mixture of an mdeniccompound and a phenolic compound,said products being viscous oils, distilling at a. high

